The Shikimic Acid Pathway

347 Pages·1986·7.1 MB·English

by  Ulrich Weiss (auth.)

recent advances in phytochemistry
volume 20
The Shikimic
Acid Pathway
RECENT ADVANCES IN PHYTOCHEMISTRY
Proceedings of the Phytochemical Society of North America
General Editor: Eric E. Conn, University of California, Davis, California
Recent Volumes in the Series
Volume 12 Biochemistry of Plant Phenolics
Proceedings of the JOint Symposium of the Phytochemical Society of
Europe and the Phytochemical Society of North America, Ghent, Belgium,
August, 1977
Volume 13 Topics in the Biochemistry of Natural Products
Proceedings of the First Joint Meeting of the American Society of
Pharmacognosy and the Phytochemical Society of North America,
Stillwater, Oklahoma, August, 1978
Volume 14 The Resource Potential in Phytochemistry
Proceedings of the Nineteenth Annual Meeting of the Phytochemical SoCiety
of North America, Dekalb, Illinois, August, 1979
Volume 15 The Phytochemistry of Cell Recognition
and Cell Surface Interactions
Proceedings of the First Joint Meeting of the Phytochemical Society of
North America and the American Society of Plant Physiologists,
Pullman, Washington, August, 1980
Volume 16 Cellular and Subcellular Localization in Plant Metabolism
Proceedings of the Twenty-first Annual Meeting of the Phytochemical Society
of North America, Ithaca, New York, August, 1981
Volume 17 Mobilization of Reserves in Germination
Proceedings of the Twenty-second Annual Meeting of the Phytochemical
Society of North America, Ottawa, OntariO, Canada, August, 1982
Volume 18 Phytochemical Adaptations to Stress
Proceedings of the Twenty-third Annual Meeting of the
Phytochemical Society of North America, Tucson, Arizona, July, 1983
Volume 19 Chemically Mediated Interactions between Plants and
Other Organisms
Proceedings of the Twenty-fourth Annual Meeting of the Phytochemical Society
of North America, Boston, Massachusetts, July, 1984
Volume 20 The Shikimic Acid Pathway
Proceedings of the Twenty-fifth Annual Meeting of
the Phytochemical Society of North America, Pacific Grove,
California, June, 1985
A Continuation Order Plan is available for this series. A continuation order will bring delivery of
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recent advances in phytochemistry
volume 20
The Shikimic
Acid Pathway
Edited by
Eric E. Conn
University of California, Davis
Davis, California
PLENUM PRESS. NEW YORK AND LONDON
Ubrary of Congress Cataloging in Publication Data
Phytochemical Society of North America. Meeting (25th: 1985: Pacific Grove, Ca.)
The shikimic acid pathway.
(Recent advances in phytochemistry; v. 20)
"Proceedings of the twenty-fifth Annual Symposium of the Phytochemical Society of
North America ... held June 12-16, 1985, at Asilomar Convention Center, Pacific
Grove, California.
Bibliography: p.
Includes index.
1. Shikimic acid-Metabolism-Congresses. 2. Amino acids-Metabolism
Congresses. 3. Plants-Metabolism-Congresses. I. Conn, Eric E. II. Title. III. Series.
QK861.R38vol. 20 581.19'2s[581.1'33] 86-8885
[QK898.S55]
ISBN-13: 978-1-4684-8058-0 e-ISBN-13: 978-1-4684-8056-6
001: 10.1007/978-1-4684-8056-6
Proceedings of the Twenty-fifth Annual Symposium of the Phytochemical Society
of North America, honoring the founders, Ted Geissman and Gestur Johnson,
held June 12-16, 1985, at Asilomar Convention Center, Pacific Grove, California
© 1986 Plenum Press, New York
Softcover reprint of the hardcover 1s t edition 1986
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No part of this book may be reproduced, stored in a retrieval system, or transmitted
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PREFACE
This volume contains the invited papers presented as a
symposium of The Phytochemical Society of North America
which met for its annual meeting at the Asilomar Conference
Center, Pacific Grove, California on June 12-16, 1985. The
topic of the symposium, "The Shikimic Acid Pathway - Recent
Advances", was especially appropriate for this, the Silver
Anniversary of the Society because of the many natural
products derived from that pathway. The organizers of the
symposium recognized that it would not be possible to cover
all groups of compounds derived from shikimic acid and
therefore decided to omit any detailed discussion of
flavonoid compounds and lignin. Research in these two
areas has been the subject of several recent symposiums
and/or published volumes. By omitting these topics, it
was possible to devote more attention to other, equally
interesting products derived from the shikimate pathway.
Each chapter in the volume authoritat~vely speaks for
itself on an important topic. However, the reader is
invited to enjoy the lead chapter by Ulrich Weiss who
describes his role in the research on the shikimate
pathway during 1952/53. We are grateful to Dr. Weiss for
this charming account of his work carried out in the
laboratory of Dr. B.D. Davis during that period.
Those who attended the Silver Anniversary Meeting were
privileged to hear Dr. Gestur Johnson reminisce about the
founding of the Society, initially called the Plant
Phenolics Group of North America. At the annual banquet
R. Horwitz also shared with us some recollections of Dr.
Ted Geismann. Geissman and Johnson are considered by
many to be the founding fathers of Plant Phenolics Group,
renamed the Phytochemical Society of North America, in
1966. Three other members who attended that inaugural
meeting and who were also at Asilomar were S.C. Brown,
L. Jurd, and G.H.N. Towers.
v
PREFACE
The organlzlng committee of the Silver Anniversary
Meeting consisted of B.G. Chan (Chair), J.A.R. Ladyman,
V.L. Singleton and E.E. Conn. As is so often the case,
much of the labor fell on the Chair of the committee. It
is therefore a pleasure to acknowledge that much of the
success of the meeting is due to Dr. Chan. Generous
financial support for the Symposium was provided by the
Monsanto Chemical Company, FMC Corporation, Shell Devel
opment Company, E.I. duPont de Nemours and Company, Cetus
Madison Corporation, Dow Chemical Company, Eli Lilly and
Company, and Idetek, Incorporated.
As editor, I wish to thank the symposium speakers for
their participation and prompt submission of their manu
scripts. Finally, thanks are due to Ms. Billie Gabriel
for her skillful preparation of the camera-ready copy.
February, 1986 Eric E. Conn
CONTENTS
1. Early Research on the Shikimate Pathway:
Some Personal Remarks and Reminiscences • 1
Ulrich Weiss
2. The Shikimate Pathway - An Overview • . • • . •• 13
Heinz G. Floss
3. Tyrosine and Phenylalanine Biosynthesis:
Relationship Between Alternative Pathways,
Regulation and Subcellular Location . • . . 57
Roy A. Jensen
4. Specific Inhibitors as Probes into the
Biosynthesis and Metabolism of
Aromatic Amino Acids • • . . . . . . . 83
Nikolaus Amrhein
5. Synthetic Organic Chemistry and the Shikimate
Pathway: Inhibitors and Intermediates 119
Paul A. Bartlett
6. Indoleacetic Acid, Its Synthesis and
Regulation: A Basis for Tumorigenicity
in Plant Disease •••••.•• 147
Tsune Kosuge and Margaret Sanger
7. Hydroxybenzoic Acids and the Enigma
of Gallic Acid • . • • • • • • • . 163
Edwin Haslam
8. Lignans: Some Properties and Syntheses 201
Andrew Pelter
9. Biosynthesis of Iso-Chorismate-Derived
Quinones . . . . . . . . . . . . . . . 243
Eckhard Leistner
vii
viii CONTENTS
10. Naturally Occurring Quinones as
Bioreductive Alkylating Agents •••• 263
Harold W. Moore and J. Olle Karlsson
11. Biochemistry of Plant Coumarins 287
Stewart A. Brown
12. Some Structural and Stereochemical
Aspects of Coumarin Biosynthesis • 317
Davis L. Dreyer
Index . 339
Chapter One
EARLY RESEARCH ON THE SHIKIMATE PATHWAY: SOME PERSONAL
REMARKS AND REMINISCENCES
ULRICH WEISS
Laboratory of Chemical Physics
National Institute of Arthritis, Diabetes,
and Digestive and Kidney Diseases
Bethesda, Maryland 20205
The 25th Annual Conference at Asilomar, California,
June 12 - 16, 1985, was a most enjoyable and stimulating
event, which has splendidly accomplished its goal: to
provide an overview of the present state of our knowledge
of the shikimate pathway and its ramifications. As parti
cipants, we all are indebted to the organizers for the job
they did; their effort must have been great.
Having taken part, during 1952/1953, in the early
research on this biosynthetic sequence, attendance at this
conference was for me a great experience indeed. To my
regret, I have never had an opportunity since those ancient
times for making further direct contributions to the eluci
dation of the shikimate pathway. I have, however, during
all these years maintained a lively interest in the advances
of research in this field. It was, therefore, a real joy to
participate in the conference and to get a coherent picture
of the present status of our knowledge through lectures by
many of the colleagues responsible for these advances, and
of course by private discussions with old friends and new
acquaintances, a method so much more satisfying and effi
cient than having to follow the progress of research
piecemeal from the original literature.
And what progress! The few remaining gaps in our
understanding of the biosynthesis of the classical five
primary aromatic metabolites are now being closed; all the
known intermediates have been prepared by total synthesis;
the enzymes involved and their regulations have been studied
in great detail. Our knowledge of this area of biosynthesis
should thus be complete in the foreseeable future. Fortu-
2 ULRICH WEISS
nately, there is no danger of this completion meaning
the end of research on the shikimate pathway. Side-branches
of this sequence are being found in increasing numbers,
giving it additional significance: the biosyntheses via
isochorismic acid, the formation of phenylalanine and
tyrosine through arogenate rather than prephenate, and
the origin of the C,N unit present in the important
ansamycin antibiotics and in the maytansinoids will suffice
to prove the point. Perhaps the most interesting and novel
development, however, is the discovery of a number of
shikimate-derived metabolites with non-aromatic six-membered
rings; it shows that the function of the shikimate pathway
is by no means limited to the biosynthesis of aromatic
compounds. Much remains to be explored in these new areas,
and we can expect with confidence that other such novel
sequences branching off from the classical one will be
discovered. In addition, some features remain unexplored
even in the initial pathway. The old puzzle of the orlgln
of quinic acid is still unsolved; interestingly, it was not
discussed at Asilomar.
It is particularly gratifying that the research on
the shikimate pathway has also brought dividends in the
form of important practical applications, such as the
discovery that the widely used herbicide glyphosate acts
by inhibiting one of the enzymes of the common part of the
sequence, the enzyme which catalyzes the conversion of
shikimate 3-phosphate into 5-enolpyruvylshikimate 3-phosphate.
This discovery is one more example supporting my firmly held
conviction that sound exploration of new fields will eventu
ally lead to findings of practical utility, even if these
could not have been anticipated in the beginning and were by
no means the initial goal of the research. This, in my
opinion, makes the division into "fundamental" or "academic",
and "applied" research artificial, meaningless, and often
harmful.
I have been invited to remlnlsce a little about the
early days of research on the shikimate pathway, and to
attempt a brief outline of the stages of further development
to its present level. I joined the small, oddly named
"Tuberculosis Research Laboratory" of the U.S. Public Health
Service on East 69th Street in Manhattan, N.Y., on December
10, 1951, to participate in the research directed by Dr.
B.D. Davis. This work was devoted to the exploration of
biosynthetic pathways leading to the amino acids and other